DE19951635A1 - Aqueous multiphase detergent - Google Patents

Abstract

The invention relates to an aqueous multiple phase detergent containing a tenside, especially a manual dishwashing detergent, comprising at least two continuous phases. The detergent has at least one lower, aqueous phase I and an upper, aqueous phase II which is not miscible with the first, and can be temporarily converted into an emulsion by shaking. Said detergent contains more than 2 wt. % of at least one organic solvent, can be used for cleaning hard surfaces, especially crockery, and is produced by directly mixing the raw materials, then re-mixing them and finally, allowing the product to stand in order to separate the temporary emulsion.

Description

The invention relates to aqueous multiphase liquid cleaning agents, in particular Hand dishwashing liquid with at least one organic solvent Let shake emulsify temporarily, use it to clean hard surfaces chen, especially dishes, and a method for their production.

Conventional liquid aqueous cleaning agents, in particular hand dishwashing detergents, are usually present as homogeneous stable solutions or dispersions. The one Set of certain, especially hydrophobic, components in such verbs Improved cleaning performance or skin care properties can lead to this ren that this homogeneity is lost and inhomogeneous means are obtained whose Acceptance by consumers can be assessed as low. In such cases, the alternative formulation of agents that, despite their inhomogeneity, are defined and suitable for the consumer has acceptable external appearance and application form. He This is made even more difficult by today's hand dishwashing detergents cleaning performance expected by the consumer high surfactant content.

European patent application 116 422 describes a liquid hair or body shampoo with two aqueous phases, which can be temporarily dispersed into one another by shaking, and both phases being miscible with water in any ratio. The upper phase contains 8 to 25% by weight, based on the total composition, of at least one surfactant and the lower phase contains at least 6% by weight, based on the total composition, of dissolved sodium hexametaphosphate of the formula I,

in which n stands for an average of approximately 12. Optionally, in the lower phase other builder salts may be included. Furthermore, up to 2 wt .-%, based on the Total composition of alcohols such as isopropanol or ethanol for solubilization of an active ingredient or perfume.

From German Offenlegungsschriften 195 01 184, 195 01 187 and 195 01 188 (Hen kel KGaA) are known hair treatment agents in the form of a 2-phase system have an oil phase and a water phase, the oil phase on silicone oil or Paraffin oil is based and can be mixed for a short time by mechanical action.

The object of the present invention was to use homogeneously, or not at all components that are difficult to incorporate and high surfactant contents in cleaning agents, especially hand dishwashing detergents, in a defined, easy to handle and for Provide consumers with acceptable form.

The invention relates to an aqueous liquid multi-phase surfactant-containing cleaning agent agent with at least two continuous phases, the at least one lower aqueous phase I and an upper aqueous phase II immiscible with this phase has and can be temporarily converted into an emulsion by shaking, and that contains more than 2% by weight of at least one organic solvent.

The invention also relates to the use of an agent according to the invention for cleaning hard surfaces, especially dishes. Preferably that is Agents according to the invention for manual cleaning of hard surfaces, in particular for manual cleaning of dishes.

In the context of the present invention, temporary is understood to mean that 90% of the Separation of the emulsion formed by shaking in the separate phases at Tem temperatures from about 20 ° C to about 40 ° C within 2 minutes to 10 hours and the last 2% of the segregation into the phase state before shaking inside from another 15 minutes to 50 hours.  

Furthermore, within the scope of the present invention - unless expressly different executed - the use of a salt as possible as the use of the correspondie acid / base pair of the salt, which only in situ with neutralization the salt or its solution results, even if the respective alternative is not in the present teaching is always formulated explicitly. In this sense, sodium citrate and Combination citric acid / sodium hydroxide are equivalent alternatives.

Finally, within the scope of the present invention, a certain component can be added are used for different purposes, their use is given below if deliberately described repeatedly. This applies, for example, to citric acid, which is both used as acid for pH adjustment as well as phase separation aid and builder can be.

The agents according to the invention are distinguished by a high cleaning performance, in particular especially on greasy soiling, with diluted and undiluted application out. The conversion into a temporary emulsion remains even after frequent shaking reversible. Furthermore, the funds enable the stable incorporation of components, those in single-phase aqueous solutions or stable emulsions or microemulsions who are only stable when using solubilizers or emulsifiers can, especially of the hydrophobic components described below and perfume oils. In addition, the multi-phase, in particular two-phase, an improvement in chemical stability of the agent through the separation of the ingredient fen in separate phases.

Substances that also serve as ingredients of cosmetic products are listed below possibly according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature be draws. Chemical compounds have an INCI name in English, herbal ingredients are only added according to Linné in Latin so-called trivial names such as "water", "honey" or "sea salt" are also in Latin language specified. The INCI names are the International Cos metic Ingredient Dictionary and Handbook - Seventh Edition (1997) by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA, is published and more than 9,000 INCI- Names and references to more than 37,000 trade names and technical names contains drawings including the associated distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook sorts the ingredients  one or more chemical classes, for example polymeric Ethers, and one or more functions (functions), for example Surfactants - Cle ansing agents, who in turn explain it in more detail and, if applicable, also to the following is referenced.

Organic solvent

According to the invention, the agent contains at least one organic solvent. The Ge hold at least one organic solvent according to the invention is more than 2% by weight and usually not more than 30% by weight, preferably 3 to 25% by weight, in particular 5 to 20% by weight, particularly preferably 7 to 15% by weight, for example 10% by weight.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 hydrocarbons, preferably C _2-15 hydrocarbons, with one or more hydroxyl groups, preferably a hydroxy group, and optionally one or more ether functions COC, ie the carbon atom interrupting oxygen atoms.

Preferred solvents are the C _1-6 alcohols, in particular ethanol, n-propanol or iso-propanol, as well as the C _2-6 alkylene glycols and poly-C _2- optionally etherified on one side with a C _1-6 alkanol. _3- alkylene glycol ethers with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule, in particular the poly-C _2-3 alkylene glycol ether etherified on one side with a C _1-6 alkanol with an average of 1 to 9, preferably 2 to 3 , Ethylene or propylene glycol groups, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).

Exemplary solvents are the following compounds named according to INCI: Alcohol (ethanol), buteth-3, butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxy propanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyl octanol, diethylene gly col, dimethoxydiglycol, dimethyl ether, dipropylene glycol, ethoxydiglycol, ethoxyethanol, Ethyl hexanediol, glycol, hexanediol, 1,2,6-hexanetriol, hexyl alcohol, hexylene glycol, Isobutoxypropanol, isopentyl diol, isopropyl alcohol (iso-propanol), 3-methoxybutanol, Methoxydiglycol, methoxyethanol, methoxyisopropanol, methoxymethylbutanol, methoxy PEG-10, methylal, methyl alcohol, methyl hexyl ether, methyl propanediol, neopentyl gly col, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 methyl ether, pentylene glycol, PPG- 7, PPG-2-buteth-3, PPG-2 butyl ether, PPG-3 butyl ether, PPG-2 methyl ether, PPG-3  Methyl ether, PPG-2 propyl ether, propanediol, propyl alcohol (n-propanol), propylene Glycol, propylene glycol butyl ether, propylene glycol propyl ether, tetrahydrofurfuryl Alcohol, trimethylhexanol.

With aliphatic or aromatic alcohols, e.g. As methanol, ethanol, n-propanol, n-butanol, tert-butanol or phenol, or carboxylic acids, e.g. B. acetic or carbonic acid, ve rether- or -esterte monomeric or homo- or heteropolymeric, especially monomeric and homodi- and trimeric, C ₂ -C ₄ alkylene glycols are, for example, under the trade name Dowanol® from Dow Chemical as well as those sold under the trade names Arcosolv® and Arconate® by Arco Chemical, such as the products designated below with their INCI name in accordance with the International Dictionary of Cosmetic Ingredients from The Cosmetic, Toiletry, and Fragrance Association (CTFA), e.g. B. Bu toxydiglycol (Dowanol® DB), methoxydiglycol (Dowanol® DM), PPG-2 methyl ether (Do wanol® DPM), PPG-2 methyl ether acetate (Dowanol® DPMA), PPG-2 butyl ether (Dowa nol® DPnB), PPG-2 Propyl Ether (Dowanol® DPnP), Butoxyethanol (Dowanol® EB), Phenoxyethanol (Dowanol® EPh), Methoxyisopropanol (Dowanol® PM), PPG-1 Methyl Ether Acetate (Dowanol® PMA), Butoxyisopropanol (Dowanol ® PnB), Propylene Glycol Propyl Ether (Dowanol® PnP), Phenoxyisopropanol (Dowanol® PPh), PPG-3 Methyl Ether (Dowanol® TPM) and PPG-3 Butyl Ether (Dowanol® TPnB) as well as Ethoxyisopropanol (Ar cosolv® PE) , tert-butoxyisopropanol (Arcosolv® PTB), PPG-2 tert-butyl ether (Arcosolv® DPTB) and propylene carbonate (Arconate® PC), of which butoxyisopropanol (dipropylene glycol n-butyl ether, Dowanol® PnB) and in particular PPG-2 Methyl ethers (dipropylene glycol methyl ether, Dowanol® DPM) are preferred.

In a particularly preferred embodiment, the agent according to the invention contains or more organic solvents from the group ethanol, isopropanol, n- Propanol, dipropylene glycol methyl ether and butoxyisopropanol (1,2-propylene glycol-n- butyl ether), preferably ethanol, isopropanol, n-propanol and / or dipropylene glycol methyl ether, especially isopropanol and / or n-propanol.

Phases

In the simplest case, an agent according to the invention consists of a lower continuous one Chen phase, which consists of the entire phase I, and an upper continuous Phase consisting of the entire phase II. One or more continuous phases However, an agent according to the invention can also emulsify parts of another phase  Contain form, so that in such an agent, for example, phase I to a Part is present as a continuous phase I, which is the lower continuous phase of the agent represents, and in part as discontinuous phase I in the upper continu phase II is emulsified. The same applies to phase II and other continuous phases total

In a preferred embodiment of the invention, the continuous phases are I and II delimited from each other by a sharp interface.

In a particular embodiment of the invention contain one or both of the conti Nuclear phases I and II parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15 vol .-%, based on the volume of the respective continuous phase, each phase other than dispersant. The continuous phase I or II is then around Volume part reduced, which is distributed as dispersant in the other phase. Before agents are added in which phase I in amounts of 0.1 to 25% by volume, preferably 0.2 up to 15% by volume, based on the volume of phase II, is emulsified in phase II.

In a further special embodiment of the invention, in addition to the continuous Chen phases I and II part of the two phases as an emulsion of one of the two phases in the other phase before, this emulsion through two sharp interfaces, one above right and a lower one, compared to the parts of phase I not involved in the emulsion and II is delimited.

The agents according to the invention usually contain phase I and phase II in a Vo lumen ratio of 90:10 to 10:90, preferably 75:25 to 15:85, in particular 60:40 to 20:80, particularly preferably 50:50 to 25:75, most preferably 40:60 to 30: 70, for example about 1: 6 (14: 86), 1: 5 (17: 83), 1: 4 (20: 80), 1: 3 (25: 75) or 1: 2 (33: 67).

Surfactants

The agents according to the invention can contain one or more nonionic surfactant components ces, anionic, amphoteric or cationic surfactants or surfactant mixtures from one, contain several or all of these classes of surfactants. The agents contain tensides in men gene, based on the composition, usually from 1 to 45 wt .-%, preferred example 5 to 40 wt .-%, in particular 10 to 40 wt .-%, particularly preferably 2 to 35% by weight, most preferably 25 to 35% by weight, for example 28 or 33% by weight. In  In a particular embodiment, the agents according to the invention contain more than 30% by weight surfactants.

Anionic surfactants are for economic reasons and because of their performance spec particularly preferred. Surfactants from the individual groups can be Substances are used. It is preferred to use mixtures of surfactants, with advantage Mixtures of surfactants from several of the aforementioned groups to use. As Surfactant mixtures are particularly suitable in combination with an anionic or more nonionic surfactants or betaine surfactants, wherein the betaine surfactants in this connection is to be equated with the class of amphoteric surfactants. Also the joint additional use of non-ionic surfactants and beta-tensi the mixture can be advantageous for many applications.

Anionic surfactants

Anionic surfactants according to the present invention can be aliphatic sulfates such as Fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic and aromatic sulfonates such as alkane sulfonates, olefin sulfonates, ethers sulfonates, n-alkyl ether sulfonates, ester sulfonates, lingin sulfonates and alkyl benzene sulfo be nate. Fatty acid can also be used in the context of the present invention cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkanesulfonates (fat acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and the half esters of secondary alcohols (secondary alkyl sulfates) of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company available under the name DAN®, e.g. B. the products mentioned in US Pat. Nos. 5,529,724 and H 1,665, DAN® 214, a C ₁₄ -SAS with 99% 2- and 3-alkyl sulfate, DAN® 216, a C ₁₆ -SAS with 99% 2- and 3- Alkyl sulfate, and DAN® 100, a SAS with 62% 2- and 3-alkyl sulfate.

The fatty alcohol ethers are particularly preferred in the context of the present invention. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols as the reaction products of one or more alkylene oxides, preferably of ethylene oxide, with alcohols, preferably for the purposes of the present invention, the longer-chain alcohols, for example the straight-chain or branched alcohols with chain lengths from C ₇ to C ₂₁ as 2-methyl-branched C ₉ to C ₁₁ fatty alcohols with an average of 3.5 EO or the C ₁₂ to C ₁₈ fatty alcohols with 1 to 4 EO. As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Another embodiment is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Low-ethoxylated fatty alcohols (0.5 to 4 mol EO, preferably 1 to 2 mol EO) are very particularly preferred for the purposes of the present invention.

Also particularly preferred in the context of the present invention are the alkanesulfonates, in particular the secondary alkanesulfonates, which are obtained from unbranched hydrogen paraffins, in particular C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. A preferred secondary alkane sulfonate is the secondary Na-C _13-17 alkane sulfonate sold by Clariant as Hostapur® SAS 60.

While the fatty alcohol ether sulfates the secondary alkanesulfonates in terms of Cleaning performance are usually slightly superior, require agents containing alkanesulfonate in usually a smaller amount of the components Pha described below cutting tools and / or builders.

Other suitable surfactants of the sulfonate type are alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, of the kind obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products. Alkylbenzenesulfonates in the sense of the teaching according to the invention are alkylbenzenesulfonates with straight-chain or branched, saturated or unsaturated C _6-22 alkyl radicals, preferably C _8-18 alkyl radicals, in particular C _9-14 alkyl radicals, most preferably C _10-13 alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, and also as ammonium salts or mono-, di- or trialkanolammonium salts, preferably mono-, di- or triethanol and / or isopropanolammonium salts, especially mono-, di- or triethanolammonium salts, but also used as alkylbenzene sulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or trialkanol [By1] amine. Likewise, the esters of 2-sulfo fatty acids (ester sulfonates), e.g. B. the 2-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

The anionic surfactants are in the form of their alkali metal and alkaline earth metal salts, in particular sodium, potassium and magnesium salts, as well as ammonium and mono-, di-, tri- or tetraalkylammonium salts and, in the case of the sulfonates, also in the form of the acid, for. B. dodecylbenzenesulfonic acid, C ₁₀ -C ₁₃ alkylbenzenesulfonic acid and / or C ₁₀ -C ₁₄ alkylbenzenesulfonic acid used. When using sulfonic acid, this is usually in situ with one or more corresponding bases, e.g. B. alkali metal and alkaline earth metal hydroxides, especially sodium, potassium and magnesium hydroxide, and ammonia or mono-, di-, tri- or tetraalkylamine - depending on the pH of the agent to be adjusted partially or completely - neutralized to the aforementioned salts . _[By2]

The agents contain one or more anionic surfactants in amounts, based on the Composition, from 0 to 45% by weight, preferably 1 to 40% by weight, in particular 5 to 35% by weight, most preferably 10 to 30% by weight, most preferably 15 to 25% by weight, for example 20% by weight. In a preferred embodiment, this is based Anionic surfactant system (s), d. H. the proportion of anionic surfactant (s) is at least half of the total amount of surfactants, in particular even more than half of the Total amount of surfactants.

Nonionic surfactants

Suitable nonionic surfactants are, for example, C ₆ -C ₂₂ alkyl alcohol polyglycol ethers, alkyl poly glycosides and nitrogenous surfactants or also sulfosuccinic acid di-C ₁ -C ₁₂ alkyl esters or mixtures thereof, especially the first two. The compositions contain nonionic surfactants in amounts, based on the composition, of usually 0 to 30% by weight, preferably 0.1 to 25% by weight, in particular 1 to 20% by weight, particularly preferably 2 to 15% by weight .-%, most preferably 3 to 10 wt .-%, for example 4 or 9 wt .-%. Presumably nonionic surfactants with their nonionic character advantageously contribute to the fact that the individual phases are stable on average over a long period of time without z. B. form deposits, and the transfer to a temporary emulsion remains reversible even after frequent shaking.

Alkyl alcohol polyglycol ether

C ₆ -C ₂₂ alkyl alcohol polypropylene glycol / polyethylene glycol ethers are preferred known nonionic surfactants. They can be represented by the formula II, R ¹ O- (CH ₂ CH (CH ₃ ) O) _p (CH ₂ CH ₂ O) _e -H, are described in which R ^{1 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 8 to 18, in particular 10 to 16, carbon atoms, p for 0 or numbers from 1 to 3 and e for Zah len is from 1 to 20.

The C ₆ -C ₂₂ alkyl alcohol polyglycol ethers of the formula II can be obtained by addition of propylene oxide and / or ethylene oxide to alkyl alcohols, preferably to oxo alcohols, the branched chain primary alcohols obtainable by oxosynthesis, or to fatty alcohols, in particular to fatty alcohols. Typical examples are polyglycol ethers of the formula II in which R ^{1 is} an alkyl radical having 8 to 18 carbon atoms, p is 0 to 2 and e is a number from 2 to 7. Preferred representatives are, for example, C ₁₀ -C ₁₄ fatty alcohol + 1 PO + 6 EO ether (p = 1, e = 6), C ₁₂ -C ₁₆ fatty alcohol + 5.5-EO (p = 0, e = 5, 5), C ₁₂ -C ₁₈ fatty alcohol + 7 EO ether (p = 0, e = 7) and isodecanol + 6-EO (R ¹ = isomer mixture of C ₁₀ oxo alcohol residues, p = 0, e = 6) as well as their mixtures. In special mixtures, at least one representative of formula II with a linear alkyl radical R ^{1 is combined} with at least one representative of formula li with a branched alkyl radical R ¹ , for example C ₁₂ -C ₁₆ fatty alcohol + 5.5-EO and isodecanol + 6-EO. It is further preferred that the linear alkyl radical have more carbon atoms than the branched alkyl radical. C ₈ fatty alcohol + 1.2 PO + 8.4 EO, C _8-10 fatty alcohol + 5 EO, C _12-14 fatty alcohol + 6 EO and C _12-14 fatty alcohol + 3 EO and mixtures thereof are particularly preferred. Non-ionic surfactants and especially alkyl alcohol polyglycol ethers cause an increase in the volume of the lower phase.

End-capped C ₆ -C ₂₂ alkyl alcohol polyglycol ethers can also be used, ie compounds in which the free OH group in the formula II is etherified. The end-capped C ₆ -C ₂₂ alkyl alcohol polyglycol ethers can be obtained by the relevant methods of preparative organic chemistry. C ₆ -C ₂₂ -Alkyl alcohol polyglycol ethers are preferably reacted in the presence of bases with alkyl halides, in particular butyl or benzyl chloride. Typical examples are mixed ethers of the formula II in which R ^{1 is} an industrial fatty alcohol residue, preferably C _12/14 coconut alkyl residue, p is 0 and e is 5 to 10, which are sealed with a butyl group.

Alkyl polyglycosides

Preferred nonionic surfactants are furthermore alkyl polyglycosides (APG) of the formula III, R ² O [G] _x , in which R ^{2 is} a linear or branched, saturated or unsaturated alkyl radical having 8 to 22 carbon atoms, [G] is a glycosidically linked sugar radical and x stands for a number from 1 to 10. APG are non-ionic surfactants and are known substances that can be obtained using the relevant methods of preparative organic chemistry. The index number x in the general formula III indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While x must always be an integer in a given compound and here before can assume all the values x = 1 to 6, the value x for a certain alkyl glycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl glycosides with an average degree of oligomerization x of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl glycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6. Xylose, but especially glucose, is preferably used as the glycosidic sugar.

The alkyl or alkenyl radical R ² (formula III) can be derived from primary alcohols having 8 to 22, preferably 8 to 14, carbon atoms. Typical examples are capronal alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.

However, the alkyl or alkenyl radical R ² is preferably derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol. Elaidyl alcohol, petroselinyl alcohol, arachidyl alcohol, Gado leyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures should also be mentioned.

Nitrogen-containing non-ionic surfactants

Suitable nitrogen-containing nonionic surfactants are, for example, amine oxides, Polyhydroxy fatty acid amides, for example glucamides, and ethoxylates of alkylamines, vicinal diols and / or carboxamides, the alkyl groups with 10 to 22 carbon atoms, preferably have 12 to 18 carbon atoms. The degree of ethoxylation of these compounds is usually between 1 and 20, preferably between 3 and 10. Preferred are ethanolamide derivatives of alkanoic acids with 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The particularly suitable compounds include lauric acid, Myristic acid and palmitic acid monoethanolamides.

Amine oxides

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy the formula R ¹ R ² R ³ N ⁺ -O ^- , in which R ^{1 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical , For example, a saturated C _12-14 -alkyl radical, in the alkylamido amine oxides via a carbonylamidoalkylene group -CO-NH- (CH ₂ ) _z - and in the alkoxy alkylamine oxides via an oxaalkylene group -O- (CH ₂ ) _z - to the nitrogen atom N is bonded to, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular re 3, and R ² and R ³ independently of one another are an optionally hydroxy-substituted C _1-4 -alkyl radical such as, for. B. is a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco Morpholine oxides, decylamine oxides, decyltetradecylamine oxides, diaminopyrimidines Oxide, Dihydroxyethyl C8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypro pylamine oxides, dihydroxyethyl C12-15 alkoxypropylamine oxides, dihydroxyethyl coca mine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamine oxides, dihy droxyethyl Tallowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Tallowamine Oxide, Hydroxyethyl Hydroxypropyl C12-15 Alkoxypropylamine Oxide, Isostearamidopropylamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramidopro pylamine oxides, lauramine oxides, methyl morpholine oxides, milkamidopropyl amines oxi de, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide,  Myristyl / Cetyl Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopro pylamine oxides, palmitamidopropylamine oxides, palmitamine oxides, PEG-3 lauramines Oxides, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphospho nomethylamine oxides, sesamidopropylamine oxides, soyamidopropylamine oxides, stea ramidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowa mine oxides, Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxi de. Preferred amine oxide (s) are, for example, cocamine oxides (N-cocoalkyl N, N-dimethylamine oxide), dihydroxyethyl tallowamine oxides (N-tallow alkyl-N, N- dihydroxyethylamine oxide) and / or cocamidopropylamine oxides (cocoamidopropyla minoxid), in particular cocamidopropylamine oxides.

Polyhydroxy fatty acid amides

Other suitable surfactants are polyhydroxy fatty acid amides of the formula III,

in the RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for water, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups . The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula IV,

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then, for example according to the teaching of international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In a preferred embodiment, the agents according to the invention contain one or more nonionic surfactants, preferably alkyl polyglycosides and / or C ₆ -C ₂₂ alkyl alcohol polyglycol ethers.

Amphoteric surfactants

Suitable amphoteric surfactants (zwitterionic surfactants) are, for example, betaines, alkylamines doalkylamines, alkyl substituted amino acids, acylated amino acids or biosurfactants, from to whom betaines are preferred in the context of the teaching according to the invention.

Betaine

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazoliniumbetaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (R ^A ) (R ^B ) (R ^C ) N ⁺ CH ₂ COO ^- , in which R ^{A is} one alkyl radicals which are optionally interrupted by heteroatoms or heteroatom groups and have 8 to 25, preferably 10 to 21, carbon atoms and R ^B and R ^{C are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaines and C ₁₁ -C ₁₇ Alkylamidopropyldimethylcarboxymethylbetaines, or formula A,

R ^I - [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ^II ) (R ^III ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y ^- (A)

in which R ^{I is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
X NH, NR ^IV with the C _1-4 alkyl radical R ^IV , O or S,
n is a number from 1 to 10, preferably 2 to 5, in particular 3,
x 0 or 1, preferably 1,
R ^II , R ^III independently of one another are a C _1-4 alkyl radical, optionally hydroxy-substituted such as, for. B. a hydroxyethyl radical, but especially a methyl radical,
m is a number from 1 to 4, in particular 1, 2 or 3,
y 0 or 1 and
Y COO, SO ₃ , OPO (OR ^V ) O or P (O) (OR ^V ) O, where R ^{V is} a hydrogen atom H or a C _1-4 alkyl radical.

The alkyl and alkyl amido betaines, betaines of formula A with a carboxylate group (Y ^- = COO ^- ), are also called carbobetaines.

Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamido betaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4,

R ^I -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (A1)

R ^I -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (A2)

R ^I -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (A3)

R ^I -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (A4)

in which R ^{I has} the same meaning as in formula A.

Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobe TAINE of the formula A1 and A2, most preferably the alkyl amido betaines of the formula A2.

Examples of suitable betaines and sulfobetaines are the following named according to INCI Compounds: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, Avocadamido propyl betaine, babassuamidopropyl betaine, behenamidopropyl betaine, behenyl betai ne, betaines, canolamidopropyl betaine, capryl / capramidopropyl betaine, carnitine, cetyl Betaines, cocamidoethyl betaines, cocamidopropyl betaines, cocamidopropyl hydroxysul taine, coco-betaine, coco-hydroxysultaine, coco / oleamidopropyl betaine, coco Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG betaines, erucamidopropyl hydroxysultaine, hydrogenated tallow betaines, isosteara midopropyl betaine, lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaines, myristyl betaines, oleamidopropyl betaines, oleamidopropyl hydroxysultaine, oleyl Betaine, olivamidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, Palmitoyl Carnitine, Palm Kernelamidopropyl Betaine, Polytetrafluoroethylene Acetoxypropyl  Betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, soyamidopropyl Betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallo wamidopropyl hydroxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecy lenamidopropyl betaine and wheat germamidopropyl betaine. A preferred ampho Surfactant is cocamidopropyl betaine (cocoamidopropyl betaine). A particularly preferred one Amphoteric surfactant is Capryl / Capramidopropyl Betaine (CAB), for example, under the Trade name Tegotens® B 810 is available from Th. Goldschmidt AG.

Alkylamidoalkylamines

The alkylamidoalkylamines (INCI alkylamido alkylamines) are amphoteric surfactants of the formula B

R ^VI -CO-NR ^VII - (CH ₂ ) _i -N (R ^VIII ) - (CH ₂ CH ₂ O) _j - (CH ₂ ) _k - [CH (OH)] _l -CH ₂ -Z-OM ( B)

in which R ^{VI is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{VII is} a hydrogen atom H or a C _1-4 alkyl radical, preferably H,
i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
R ^{VIII is} a hydrogen atom H or CH ₂ COOM (to M su),
j is a number from 1 to 4, preferably 1 or 2, in particular 1,
k is a number from 0 to 4, preferably 0 or 1,
l 0 or 1, where k = 1 if l = 1,
Z is CO, SO ₂ , OPO (OR ¹² ) or P (O) (OR ¹² ), where R ^{12 is} a C _1-4 alkyl radical or M (see below), and
M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas B1 to B4,

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ -COOM (B1)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ CH ₂ -COOM (B2)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -SO ₃ M (B3)

R ^VI -CO-NH- (CH ₂ ) ₂ -N (R ^VIII ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (B4)

in which R ^VI , R ^VIII and M have the same meaning as in formula B.

Exemplary alkylamidoalkylamines are the following compounds named according to INCI gen: Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate, DEA-Cocoampho dipropionate, disodium caproamphodiacetate, disodium caproamphodipropionate, diso dium capryloamphodiacetate, disodium capryloamphodipropionate, disodium cocoam phocarboxyethylhydroxypropylsulfonate, disodium cocoamphodiacetate, disodium coco amphodipropionate, disodium isostearoamphodiacetate, disodium isostearoamphodipro pionate, disodium laureth-5 carboxyamphodiacetate, disodium lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2- Isodeceth-7 carboxyamphodiacetate, disodium stearoamphodiacetate, disodium tallo wamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfo nate, sodium caproamphopropionate, sodium capryloamphoacetate, sodium caprylo amphohydroxypropyl sulfonates, sodium capryloamphopropionate, sodium cocoamphoa cetate, sodium cocoamphohydroxypropyl sulfonate, sodium cocoamphopropionate, So dium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoampho propionate, Sodium Lauroamphoacetate, Sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsul fonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearo amphoacetate, sodium stearoamphohydroxypropylsulfonate, sodium stearoamphopro pionate, sodium tallamphopropionate, sodium tallowamphoacetate, sodium undecy lenoamphoacetate, sodium undecylenoamphopropionate, sodium wheat germamphoa cetate and Trisodium Lauroampho PG Acetate Chloride Phosphate.

Alkyl substituted amino acids

Alkyl-substituted amino acids preferred according to the invention (INCI alkyl-substituted amino acids) are monoalkyl-substituted amino acids according to formula C,

R ^IX -NH-CH (R ^X ) - (CH ₂ ) _u -COOM '(C)

in which R ^{IX is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{X is} a hydrogen atom H or a C _1-4 alkyl radical, preferably H,
u is a number from 0 to 4, preferably 0 or 1, in particular 1, and
M 'is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine,
alkyl-substituted imino acids according to formula D,

R ^XI -N - [(CH ₂ ) _v -COOM "] ₂ (D)

in which R ^{XI is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
M "is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups can have the same or two different meanings, e.g. B. can be hydrogen and sodium or twice sodium,
and mono- or dialkyl-substituted natural amino acids according to formula E,

R ^XII -N (R ^XIII ) -CH (R ^XIV ) -COOM '''(E)

in which R ^{XII is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 alkyl radical,
R ^{XIII is} a hydrogen atom or a C _1-4 alkyl radical, optionally hydroxyl- or amine-substituted, e.g. B. a methyl, ethyl, hydroxyethyl or aminopropyl radical,
R ^XIV the residue of one of the 20 natural α-amino acids H ₂ NCH (R ^XIV ) COOH, and
M '''is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. B. protonated mono-, di- or triethanolamine.

Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula C1,

R ^IX -NH-CH ₂ CH ₂ COOM '(C1)

in which R ^IX and M 'have the same meaning as in formula C.

Exemplary alkyl substituted amino acids are the following named according to INCI Compounds: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic  Acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Stea riminodipropionate, disodium tallowiminodipropionate, lauraminopropionic acid, lauryl Aminopropylglycine, lauryl diethylenediaminoglycine, myristaminopropionic acid, sodium C12-15 alkoxypropyl iminodipropionate, sodium cocaminopropionate, sodium laura minopropionate, sodium lauriminodipropionate, sodium lauroyl methylaminopropionate, TEA lauraminopropionate and TEA myristaminopropionate.

Acylated amino acids

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids, which carry the acyl radical R ^XV CO of a saturated or unsaturated fatty acid R ^XV COOH on the amino nitrogen atom, where R ^{XV is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _{8 -18} -alkyl radical, in particular a saturated C _10-16 -alkyl radical, for example a saturated C _12-14 -alkyl radical. The acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, e.g. B. mono-, di- or triethanolammonium salt can be used. Exemplary acylated amino acids are the acyl derivatives summarized according to INCI under amino acids, e.g. B. Sodium Cocoyl Glutamate, Lauroyl Glutamic Acid, Capryloyl Glycine or Myristoyl Methylalanine.

The agents contain one or more amphoteric surfactants, especially alky lamidobetaines, in amounts, based on the composition, of 0 to 15% by weight, preferably 0.1 to 10% by weight, in particular 1 to 8% by weight, particularly preferably of 2 to 6% by weight, most preferably 3 to 5% by weight, for example 4% by weight.

In a particularly preferred embodiment of the invention, the agents contain a or more anionic surfactants together with one or more nonionic ones and / or one or more amphoteric surfactants, preferably one or more anio African surfactants and one or more nonionic surfactants, in particular one or more more anionic, one or more nonionic and one or more amphoteric tensi de.

Hydrophobic components

In a particularly advantageous embodiment of the invention, the agents contain one or more hydrophobic components. The hydrophobic components do not improve only the cleaning effect against hydrophobic contaminants such as grease dirt  and / or the skin care effect, but also have a positive effect on the phases separation and their reversibility. Here the defined inhomogeneous form of Multi-phase agents according to the invention a stable incorporation - in particular also in larger amounts - the hydrophobic components, which are in single-phase aqueous solutions or stable emulsions or microemulsions only through the use of solvents agents or emulsifiers are usually incorporated in a very limited amount in a stable manner can.

Suitable hydrophobic components are, for example, dialkyl ethers with identical or different C ₄ to C ₁₄ alkyl radicals, in particular linear dioctyl ether; Hydrocarbons with a boiling range of 100 to 300 ° C, especially 140 to 280 ° C, for. B. aliphatic hydrocarbons with a boiling range of 145 to 200 ° C, isoparaffins with a boiling range of 200 to 260 ° C; essential oils, in particular limonene and pine oil extracted from pine roots and stumps; and also mixtures of these hydrophobic components, in particular mixtures of two or three of the hydrophobic components mentioned.

Preferred mixtures of hydrophobic components are mixtures of different Dialkyl ethers, of dialkyl ethers and hydrocarbons, of dialkyl ethers and etheri oils, hydrocarbons and essential oils, dialkyl ethers and Koh Hydrogen oils and essential oils and of these mixtures.

Particularly preferred hydrophobic components are the skin-care dialkyl ethers, especially di-n-octyl ether.

The agents contain hydrophobic components in amounts, based on the combination settlement, from 0 to 20% by weight, preferably 0.1 to 15% by weight, in particular 1 to 12% by weight, particularly preferably 2 to 10% by weight, extremely preferably 3 to 8% by weight, for example 4 to 6% by weight, e.g. B. 5% by weight.

Phase separation aid

The agents according to the invention can contain one or more phase separation aids. Suitable phase separation aids are, for example, the alkali metal and alkaline earth metal halides, in particular chlorides and sulfates and nitrates, in particular sodium and potassium chloride and sulfate, and also ammonium chloride and sulfate or mixtures thereof. Such salts assist as - increasing the ionic strength - strong electrolytes the phase separation by the salt effect. A particularly preferred phase separation aid are magnesium salts of the above-mentioned anions, in particular magnesium chloride, for example in the form of its hexahydrate MgCl ₂ .6H ₂ O, since the magnesium ions additionally improve the skin-friendliness and, as a degreaser, the cleaning performance.

The ionic or saline builders described below also act as Phase separation aids, so that in their presence either less or none at all additional phase separation aid is required.

Builder

Furthermore, the agent according to the invention preferably contains one or more builders, especially to improve cleaning performance. Suitable builders are at for example alkali metal citrates, gluconates, nitrilotriacetates, carbonates and bicarbonates, especially sodium citrate, gluconate, and nitrilotriacetate, as well as sodium and potassium car bonate and bicarbonate, and alkali metal and alkaline earth metal hydroxides, in particular Sodium and potassium hydroxide, ammonia and amines, especially the alkanolamines Mo no-, di- and triethanolamine, or mixtures thereof. This also includes the salts of Glutaric acid, succinic acid, adipic acid, tartaric acid and benzene hexacarboxylic acid as well Aminotrimethylenephosphonic acid, hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1- diphosphonic acid, ethylenediamine tetra (methylenephonic acid), diethylenetriamine penta (me ethylene phosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid and phosphonates. Phos In contrast, phates are less suitable; for example, this leads as sodium tripolyphos Commonly known pentasodium triphosphate (NaTPP) often leads to severe precipitation.

If the builder is also to act as a pH-stabilizing buffer, alkali metal and Alkaline earth metal carbonates and bicarbonates, preferably sodium carbonate (soda), before increases, especially together with citric acid or - if necessary in situ from citric acid and hydroxide generated - citrate, e.g. B. sodium or potassium citrate, particularly preferred together with the mixture of citric acid or citrate described above.

In the context of the present invention, the citrates are - if not expressly stated otherwise - around the salts of the triple deprotonated citric acid re. However, the mono- and dihydrogen citrates can also be used according to the invention.

The builder salts mentioned can also be used in the form of their corresponding acids or bases, which are then partially or completely neutralized depending on the pH to be set. The acids mentioned can also be used in the form of their salts, preferably their alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkanolammonium salts, in particular mono-, di- or triethanolammonium salts, or mixtures thereof, in particular their sodium salts are, for example citric acid in the form of its monohydrate citric acid.1H ₂ O instead of citrate. The builder salts also act as phase separation aids. The complexing builders also serve in particular to ensure a clear application solution when using the agents with hard water.

Citric acid or citrates are particularly preferred builders. Preferred is - optionally generated in situ from citric acid and hydroxide or alkanolamine - citrate from the Group of alkali metal, alkaline earth metal, ammonium and mono-, di- or trialkano lammonium citrates, preferably mono-, di- or triethanolammonium citrates, or their Mixtures, especially sodium citrate and / or potassium citrate, particularly preferably Mo noethanolammonium citrate, since citrates are inherently builder and phase separation aids unite in a particularly advantageous manner and also remove Promote lime dirt.

In a particular embodiment, the agent according to the invention contains citric acid or citrate and magnesium chloride, especially monoethanolammonium citrate and magne sium chloride.

The agents contain builders and / or phase separation aids in a total amount, bezo gene on the composition, preferably 1 to 40 wt .-%, in particular 5 to 35% by weight, particularly preferably 10 to 31% by weight, extremely preferably 15 to 25% by weight.

Perfume oils

The agent according to the invention preferably also contains one or more perfume oils, because in addition to the fragrance, they support phase separation and cleaning performance improve. Perfume oils in particular prepare for incorporation, especially larger ones Quantities, in single-phase aqueous solutions or stable emulsions or microemulsions regularly problems and make use of solubilizers or emulsifiers required, but without being able to stabilize larger perfume oil contents. Here comes the great advantage of the defined inhomogeneous form of the multiphase according to the invention  Means to wear, the stable incorporation of the perfume oils, especially in larger quantities.

The components of the suitable perfume oils described in the following are in Klam Subordinated numbers, e.g. B. "(5.0)", which are exemplary An gave the composition of the respective perfume oil in% by weight, based on the Perfume oil. So "Geraniol (105.0)" means that the perfume oil Geraniol z. B. in one May contain amount of 105.0 wt .-%.

Dyna, for example, contains a suitable perfume oil with a fresh, fruity fragrance scone 10 (5.0), cyclovertal (7.5), hexyl acetate (35.0), allyl heptanoate (200.0), amyl butyrate (5.0), Prenylacetate (10.0), Aldehyde C 14 SOG (70.0), Manzanate (15.0), Melusate (30.0), Ortho tert butylcyclohexyl acetate (200.0), cinnamaldehyde (5.0), isobomylacetate (10.0), dihy drofloriffone TD (2.5), Floramat (100.0), phenylethyl alcohol (30.0), geraniol (105.0), Cy clohexyl salicylate (150.0) and citronellol (20.0).

A suitable perfume oil with a fresh, floral fragrance contains, for example, Ber gamotte oil (250.0), lemon oil Messina (50.0), citronellal (2.0), orange oil sweet (50.0), Lavender oil (50.0), terpineol (50.0), lilial (100.0), phenylethyl alcohol (80.0), citronellol (100.0), geraniol (20.0), benzyl acetate (60.0), isoraldein 70 (50.0), ylang (30.0), ambroxan 10% in IPM (1.0), Heliotropin (47.0) and Habanolide (60.0).

A suitable perfume oil with an aromatic fragrance contains, for example, orange oil (710.0), α-pinene (130.0), β-pinene (20.0), γ-terpinene (95.0) and Litsea Cubeba oil (55.0).

The content of one or more perfume oils is usually 0.1 to 15% by weight, preferably 0.2 to 10% by weight, in particular 0.5 to 5% by weight, particularly preferably 1 up to 2% by weight.

Enzymes

In a particular embodiment of the invention, the agent contains one or more Enzymes.

The enzymes customary in detergents and cleaning agents are suitable, for example Proteases (e.g. BLAP 260 L®, BLAP S 260 SLD®, BLAP S 260 ALD®, BLAP S 260 LD® and BLAP S 260® from Biozym or Durazym®, Savinase® and Alcalase® from Novo Nordisk), amylases (e.g. Termamyl® from Novo Nordisk), cellulases (e.g. KAC 500®  from Kao, Celluzyme® from Novo Nordisk), lipases (e.g. Lipolase 100 L® and Lipola se 100 T® from Novo Nordisk) and peroxidases and reductases.

The nonionic surfactants in general and the alkyl polyglycosides in particular improve the storage stability of the enzyme-containing embodiment, as do the citric acid or its salts and also the hydrophobic components, in particular the - if etherified or esterified - mono- or polymeric C ₂ -C ₄ Alkylene glycols, e.g. B. the products sold under the trade names Dowanol®, Arcosolv® and Arconate® as well as polyethylene glycols and their derivatives. Here, the multiphase liquid according to the invention has an advantageous effect on the stability of the enzymes, which is presumably due to the enrichment of the enzymes in the rich in the aforementioned stabilizing components and - in terms of ionic strength - less ionic upper phase II.

PH value

The pH of the agents according to the invention can - in adaptation to the particular type intended use - over a wide range from strong acidity to neutrality to highly alkaline can be varied, preferably in a range from 1 to 12, in particular 2 until 11.

Suitable pH regulators are, on the one hand, acids such as the mineral acids, e.g. B. hydrochloric acid, but especially citric acid, and on the other hand the aforementioned alkaline builders, preferably sodium hydroxide, potassium hydroxide and alkanolamines, especially Mo noethanolamine.

In an alkaline embodiment of the invention, the agents have a pH of over 7 to 12, preferably 8 to 11, in particular 8 to 10.5, for example between rule 8 and 9, z. B. 8.3, for moderate alkalinity or over 9 to 10.5, 11 or even 12, e.g. B. 10, for stronger alkalinity.

In a preferred embodiment of the invention, in particular for manual dishwashing, the agents are neutral to acidic with a pH of 3 to 7, preferably 3.5 to 7, in particular 4 to 6.5, particularly preferably 4.5 to 6.5, most preferably 5 to 6, for example 5.5. To set such a pH, the agents contain at least one acid. Inorganic acids, for example the mineral acids, for. As hydrochloric acid, and organic acids, for example saturated or unsaturated C _1-6 mono-, di and tricarboxylic acids and hydroxycarboxylic acids with one or more hydroxy groups, e.g. B. citric acid, maleic acid, formic acid and acetic acid, amidosulfuric acid, C _6-22 fatty acids and anionic sulfonic acids, and mixtures thereof, e.g. B. the succinic acid-glutaric acid-adipic acid mixture available from BASF under the trade name Sokalan® DCS. Particularly preferred acids are citric acid, preferably used in the form of its monohydrate citric acid.1H ₂ O, and the anionic sulfonic acids and combinations of citric acid with one or more anionic sulfonic acids, in particular with alkylene sulfonic acids. Citric acid advantageously combines acid, builder and phase separation auxiliary properties, while the anionic sulfonic acids act simultaneously as an acid and an anionic surfactant. If necessary, one or more alkalis can additionally be used, for example the alkali metal, alkaline earth metal and ammonium hydroxides and carbonates, and ammonia or amines, preferably sodium and potassium hydroxide and alkanolamines, monoethanolamine being particularly preferred.

To stabilize or buffer the pH, the agent according to the invention contains in a special embodiment, small amounts of corresponding buffer substance zen, in the alkaline embodiment described, for example soda or natri umbicarbonate.

Thickener

To adjust the viscosity, the agent according to the invention can have one or more ver thickener, preferably in an amount of 0.01 to 5% by weight, in particular 0.05 up to 2.5% by weight, particularly preferably 0.1 to 1% by weight.

Suitable thickeners are organic natural thickeners (agar-agar, Carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust beans bread flour, starch, dextrins, gelatin, casein), organic modified nature substances (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, powdered meal ether), organic fully synthetic thickeners (Polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyes ther, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas).  

The polyacrylic and polymethacrylic compounds include, for example, the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association ( CTFA): Carbomer), which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from BFGoodrich under the trade name Carbopol®, e.g. B. Carbopol® 940 (molecular weight approx.4,000,000), Carbo pol® 941 (molecular weight approx.1,250,000) or Carbopol® 934 (molecular weight approx.3,000,000). The following also include the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters (INCI acrylates copolymer), preferably formed with C _1-4 alkanols, to which, for example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which, for example, from Rohm & Haas under the trade names Aculyn ® and Acusol® are available, e.g. B. the anionic non-associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acu sol® 830 (CAS 25852-37-3); (ii) Crosslinked high molecular acrylic copolymers, for example the copolymers of C _10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple, preferably with C _{1 -4} -alkanols ge formed, ester (INCI Acrylates / C10-30 alkyl acrylate crosspolymer) and which are available for example from BFGoodrich under the trade name Carbopol®, for. B. the hydrophobized Carbopol® ETD _[By3] 2623 and Carbopol® 1382 (INCI Acryla tes / C10-30 Alkyl Acrylate Crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX _[By4] 473).

Preferred thickeners are the polysaccharides and heteropolysaccharides, in particular especially the polysaccharide gums, for example gum arabic, agar, alginates, car rageene and its salts, guar, guaran, tragacant, gellan, ramsan, or dextran Xanthan and its derivatives, e.g. B. propoxylated guar, and their mixtures. Other buttocks Alternatively, lysaccharide thickeners such as starches or cellulose derivatives can be preferred but can be used in addition to a polysaccharide rubber, for example starches various origin and starch derivatives, e.g. B. hydroxyethyl starch, starch phos phate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl,  Ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.

A particularly preferred polymer is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 × 10 ⁶ and is available, for example, from Kelco under the trade name Keltrol®, e.g. B. as cream-colored powder Keltrol® T (Transparent) or as white granulate Keltrol® RD (Readily Dispersable).

In a preferred embodiment, the agent according to the invention is free from Ver thickeners.

Auxiliaries and additives

In addition to the components mentioned, the agents according to the invention can contain further auxiliaries. and contain additives as are customary in such agents. These include in particular special polymers, soil release agents, solubilizers, hydrotropes (e.g. sodium cumene sulfonate, octyl sulfate, butyl glucoside, butyl glycol), emulsifiers (e.g. gallic soap), Gloss drying additives, cleaning enhancers, antimicrobial agents or disinfectants agents, antistatic agents, preservatives (e.g. glutaraldehyde), bleaching systems and Dyes and opacifiers or skin protection agents, as described in EP-A-522 556 are described. The amount of such additives is usually not over 12% by weight in the detergent. The lower limit of the bet depends on the type of Auxiliary and additive and can, for example, with dyes up to 0.001 wt .-% and below. The amount of auxiliaries and additives is preferably between between 0.01 and 7% by weight, in particular 0.1 and 4% by weight.

A preferred auxiliary and additive are dyes, because their phases add them can be colored differently what the visual perception of the separated Phases as well as tracking of emulsion formation or separation easier, and so the handling of the agent is made even easier.

The agents according to the invention can be mixed directly from their raw material then mix and then stand to stand Temporary emulsion can be prepared. Another object of the invention is accordingly a method for producing an agent according to the invention  by mixing directly from its raw materials, then mixing and finally standing the means for separating the temporary emulsion.  

Examples

Agents E1 to E6 according to the invention were produced. Table 1 shows the Composition shown in wt .-%.

Table 1

All means showed two clear continuous phases, which were temporary when shaken formed an emulsion. Even after repeated shaking, the standing glass formed separate phases again.

Claims (18)

1. Aqueous liquid multi-phase surfactant-containing cleaning agent, in particular hand dishwashing detergent, with at least two continuous phases, which has at least a lower aqueous phase I and an immiscible upper phase II with this phase and can be temporarily converted into an emulsion by shaking, thereby characterized in that it contains more than 2 wt .-% of at least one organic solvent. 2. Composition according to claim 1, characterized in that there is at least one organi chemical solvent in an amount of more than 2 to 30 wt .-%, preferably 3 up to 25% by weight, in particular 5 to 20% by weight, particularly preferably 7 to 15% by weight. 3. Agent according to one of claims 1 or 2, characterized in that one or several organic solvents from the group ethanol, isopropanol, n-propanol, Dipropylene glycol methyl ether and butoxyisopropanol, especially isopropanol and / or n-propanol. 4. Agent according to one of claims 1 to 3, characterized in that the conti Nuclear phases I and II abge against each other by a sharp interface are limited. 5. Agent according to one of the preceding claims, characterized in that a or both of the continuous phases I and II parts, preferably 0.1 to 25% by volume, in particular 0.2 to 15% by volume, based on the volume of the respective continuous Chen phase, the other phase contain as dispersant. 6. Agent according to one of the preceding claims, characterized in that Phase I in amounts of 0.1 to 25% by volume, preferably 0.2 to 15% by volume, based on the volume of phase II is emulsified in phase II. 7. Agent according to one of the preceding claims, characterized in that ne ben the continuous phases I and II part of the two phases as an emulsion ner of the two phases is present in the other phase, this emulsion by two sharp interfaces, an upper and a lower, compared to the ones not on the Emulsion involved parts of phases I and II is delimited.   8. Agent according to one of the preceding claims, characterized in that it Phase I and Phase II in a volume ratio of 90:10 to 10:90, preferably way 75: 25 to 15: 85, in particular 60: 40 to 20: 80, contains. 9. Agent according to one of the preceding claims, characterized in that it contains one or more anionic surfactants. 10. Agent according to one of the preceding claims, characterized in that it contains one or more nonionic surfactants, preferably alkyl polyglycosides C _6-22 - and / or alkyl alcohol polyglycol ethers. 11. Agent according to one of the preceding claims, characterized in that it contains one or more amphoteric surfactants. 12. Agent according to one of the preceding claims, characterized in that it additionally contains hydrophobic components from the group of dialkyl ethers with identical or different C ₄ - to C ₁₄ -alkyl radicals, in particular dioctyl ether, of hydrocarbons with a boiling range from 100 to 300 ° C, in particular 140 to 280 ° C, the essential oils, in particular limonene and pine oil, and their mixtures, in particular mixtures of two or three of the hydrophobic components mentioned. 13. Agent according to one of the preceding claims, characterized in that it additionally one or more phase separation aids, in particular magnesium chloride, contains. 14. Agent according to one of the preceding claims, characterized in that it additionally one or more builders, preferably citric acid or citrates, in particular special triethanolammonium citrate, contains. 15. Agent according to one of the preceding claims, characterized in that it contains one or more perfume oils. 16. Agent according to one of the preceding claims, characterized in that it contains one or more enzymes.   17. A method for producing an agent according to any one of the preceding claims by mixing directly from its raw materials, then mixing and finally standing the means for separating the temporary emulsion. 18. Use of an agent according to one of the preceding agent claims for cleaning hard surfaces, especially dishes.